Organo bismuth biocide



matrices an a 3.

SEAHUH HQUM 3,247,050 ORGANO BISMUTH BIOCIDE John R. Leebrick, RosellePark, N.J., assignor, by mesne assignments, to M & T Chemicals Inc., NewYork, N.Y., a corporation of Delaware No Drawing. Filed Oct. 11, 1962,Ser. No. 229,994 2%) Claims. (Cl. 16722) This application is acontinuati-on-in-part of application Serial No. 202,377 filed June 14,196 2.

This in ention relates to meth of preventing and/or inhibitmg the growthof i roorganisms, including bacteria and fungi and to compositions ofmatter utilized in these methods. The invention more particularlyrelates to materials which have been made resistant to attack bybacteria by the aforesaid methods.

It is an object of this invention to provide methods for inhibitingand/or preventing the growth of bacteria. It is also an object of thisinvention to provide methods for inhibiting and/or preventing the growthof fungi. It is another object of this invention to provide compositionswhich are useful in the aforesaid methods as the source of the activebactericidal and/or fungicidal compound (s). It is another object ofthis invention to provide bacteria and/or fungi iggistant paint- It isanother object of this invention to provid e ba'cteria and/ or fungiresistant plastics and fibrous products such as textiles and paperproducts. It is also an object of this invention to provide sanitizercompositions having particular utility in hospital treatment.

The method of this invention for protecting a medium susceptible toattack by microorganisms comprises applying to the locus to beprotected, an active amount of at least one bismuth compound having theformula R' BiX or R BiX wherein n is 1 or 2, R is an aryl group, and Ris an alkyl, cycloalkyl, alkenyl, or aryl group, and X is a largelyionic bonded atom or group, and is preferably halogen, oxygen, sulfur,carboxylate, phenoxide, alkoxide, mercaptide, or cyanide. The bismuthcompounds showing particularly the unusual activity against bacteria arethose having 1 or 2 atoms, or groups, joined to the bismuth atom bybonds having ionic characteristics. X may act as a bridging group oratom to provide his bismuth compounds which may be classified assubstituted mono bismuth compounds and are within the scope of thepresent invention as defined herein. Various R and X groups may becyclized or otherwise joined. The amount of the bismuth compoundeffective in a given application is dependent upon a number of factorswhich include the substrate -to be protected, the method of application,the degree of protection desired, the bismuth compound utilized, theenvironment, etc. The bismuth compounds have proven to be effectiveagainst a wide spectrum of bacteria including Gram negative and Grampositive bacteria. They are particularly effective against Gram negativebacteria. Certain of these compounds may be particularly characterizedby their efieetivity against fungi.

Of the pentavalent organo bismuth compounds useful in this invention,those in which R is a monocyclic aryl, as exemplified by phenyl, monoandpolychlorophenyls, tolyl, lower alkoXyphenyl-s and xylyl, are preferred.Of the monoand diorganic trivalent bismuth compounds those in which R isa monocyclic aryl are also preferred. Of these compounds in which the Rgroup is an alkyl, those having less than 19 carbon atoms in the chain,and particularly those having from 3 to 8 carbon atoms are of mostinterest. These bismuth compounds in which X is a halogen or acarboxylate are preferred. The preferred compounds include:t-riphenylbismuth dihydroxide, triphenylbismuth dichloride,triphenylbismuth diacetate, triphenylbismuth disalicylate,diphenylbismuth chloride, di-

phenylbismuth acetate, diphenylbismuth salicylate, phenylbismuthdichloride, phenylibismuth diacetate, phenylbismuth disalicylate,diphenylbismuth laurylmercaptide, triphenylbismuth dibenzoate,phenylbismuth oxide, dibutylbismuth chloride, dioctylbismutho-phenylphenate.

It is a particular feature of the invention that unexpectedly superiorinhibiting properties may be obtained by the use of compounds RBiXwherein R may be an alkyl, preferably a lower alkyl containing from 3 to8 carbon atoms, and X may be selected from the group con sisting ofhalogen, oxygen, sulfur, carboxylate, phenoxide, alkoxide, mercaptide,and cyanide. Preferred X groups may be halogen, preferably chlorine.Preferably the X groups may be the same.

Typical of the compounds which may preferably be employed in practice ofthis invention may be Methylbismuth dichloride Methylbismuth dibromideMethylbismuth diacetate Methylbismuth oxide Methylb-ismuth sulfideEthylbismuth dichloride Ethylbismuth dibromide Ethylbismuth diacetateEthylbismuth oxide Ethylbismuth sulfide Propylbismuth dichloridePropylbismuth dibromide Propylbismuth diacetate Propyl'bismuth oxidePropylbism-uth sulfide Propylbismuth diphenoxide Propylbismuthdimethoxide Butylbismuth dichloride Butylbismuth dibromide Butylbismuthdiacetate Butylbismuth sulfide Butyllbismuth diphenoxide Butylbismuthdimethoxide Butylbismuth dicyanide Butylbismuth dilaurylmercaptideIsobutylbismuth dichloride Isobutylbismuth dibromide Isobutylbismuthdiacetate Isobutylbismuth oxide Isobutylbismuth sulfide Isobutylbismuthdiphenoxide Isobutylbismuth dimethoxide Isobutylbismuth dicyanideIsobutylbismuth diphenylmercaptide n-Amylbismuth dichloriden-Amylb-ismuth dibromide n-Amylbi-smuth diacetate n-Amylbismuth oxiden-Amylbismuth sulfide n-Octylbismuth dichloride n-Octylbismuth dibromiden-Octylbism-uth diacetate n-Octylbismuth oxide n-Octylbismuth sulfideZ-ethylhexy-lbismuth dichloride Z-ethylhexylbismuth diacetate.

It is a particular feature of this invention that those compounds RBiXwherein R may be butyl are particularly effective. The preferredcompound may be'butylbismuth dichloride.

It is a feature of this invention that germicidal activity of thehereinbefore noted compositions may be enhanced even further when thebismuth compound is used in combination with substituted ammoniumcompounds wherein R" may be a hydrocarbon radical, typically alkyl,alkenyl, aryl, alkaryl, aralkyl, cycloalkyl, etc. R" may be for example,methyl, ethyl, propyl, isopropyl, n butyl, isobutyl, t-butyl, amyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, oleyl i.e. 7-heptadecenyl,etc. phenyl, m-, or p-tolyl, naphthyl, cyclohexyl, benzyl, etc.; 0 maybe an integer, 14; d may be an integer, 0-3; and the sum of c and d is4. All of the R groups need not be the same. It will be apparent that Rmay include a cyclic linkage in which more than one carbon atom may bejoined to the nitrogen atom, e.g., a polymethylene linkage, in whichcase the grouping including the nitrogen atom may be the piperidinogroups. Similarly, the pyridyl or the quinolyl group may be present,etc. A may be an anion of a complex-forming compound, i.e., a compoundwhich forms a substituted ammonium complex with an amine, as is wellknown, typically a halide, e. g., chloride, sulfate, sulfonate, acetate,etc.

The preferred compounds which may be employed include compounds of theformula R NH -A wherein c is 4 and d is O. The formula of thesepreferred quaternary ammonium compounds may be R N-A. Typical of thesepreferred quaternary ammonium compounds which may be employed may bethose formed by reacting tertiary amines typified by dimethyldodecylamine, diethyl dodecylamine, dimethyl decylamine, dimethyloctylamine, trimethyl amine, tributyl amine, triethyl amine, pyridine,etc. with halides, typified by alkyl halides such as methyl bromide,ethyl chloride, propyl bromide, methyl iodide, butyl bromide, butylchloride, amyl iodide, benzyl chloride, etc.

The preferred quaternary ammonium compound which may be employed is analkyl (e.g., lauryl) dimethyl benzyl ammonium chloride, typically thatavailable under the trademark BTC824 of Onyx Chemical Co. Other specificillustrative compounds which may be employed may include(dodecylbenzyl)pyridinium chloride; lauryl dimethyl benzylammoniumchloride; decyl dimethyl benzyla-mmoni-um chloride; etc.

The methods of this inventon may be carried out by applying the bismuthcompounds (alone or preferably with the quaternary ammonium compounds)to the surface of the material to be protected and/or admixing thebismuth compounds with the material to be protected during thefabrication of said material. The bismuth compounds may be used per se,particularly when they are incorporated into the material duringpreparation or fabrication. Many materials, and particularly fibrousproducts such as textiles, maybe treated by applying the bismuthcompound to the surface by dipping, padding, spraying, etc. They may beused in the form of a bactericidal and/or fungicidal composition inwhich the bismuth compound is the active component or one of the activecomponents. Typically the bismuth compound may be present in amount of0.l%% by weight of total mixture of carrier and bimuth compound. Liquidcompositions may be utilized in which the bismuth compound is dissolvedand/ or suspended in a solvent. Solid compositions may be utilized inwhich the bismuth compound is mixed with a carrier (or diluent). Thecarrier may be inert, such as talcs, clays, diatomaceous earth, flours,etc., or it may have activity such as that shown by the quaternaryammonium compounds. The liquid formulations of the emulsion type willoften include a dispersion agent such as the anionic, cationic ornonionic surface active agents. To obtain fungicidal and/or bactericidalcompositions having an extremely broad spectrum of activity, the bismuthcompounds may be formulated with other active materials such as thetrior-ganotins, pentachlorophenol, phenyl mercuric oleate, copper-8-quinolinolate, bisphenols, o-iphenylphenol, polybrominatedsalicylanilides, and metal (zinc) dialkyl dithiocarbamates. Illustrativeof the compositions useful for carrying the active bismuth compound areExamples 14.

Example 1.Aerosol composition 7 Parts by weight Tributyltin oxide 0.02Triphenylbismuth dichloride 0.02 Toluene 15.00 Fluorohydrocarbon gaseouspropellant 84.96 Example 2.Liquid composition Phenylbismuth disalicylate1 Water 8 Acetone 2 Lauryl dimethylben'zylammonium chloride (50%-inIllustrative useful compositions containing highly preferred activebismuth compounds RBiX are Examples 5-8.

Example 5 .Aeros0l composition Parts by weight Tributyltin oxide 0.02Butylbismuth dichloride 0.0 2 Toluene 15.00 Fl'uorohydrocarbon gaseouspropellant 84.96

7 Example 6A.Liquid composition Butylbismuth dichloride 1 Water 8Acetone- 2.

Lauryl dimethylbenzylammonium chloride (50%-in water) 10 Trisodium saltof N-hydroxyethylethylenediamine triacetic acid 0.4 Toluene 3 Example 6BAnother particularly desirable composition which may be employed using aquaternary ammonium compound may be:

Butylbismuth dichloride 1 Water 8 Acetone 2 Dodecyl pyridinium ammoniumchloride (50%-in water) l0 Trisodium salt ofN-hydroxyethylethylenediamine triacetic acid 0.4 Toluene 3 Example7.Emulsion composition Tripropyltin acetate 0.02 Propylbismuth diacetate0.02 Toluene 15.00 Non-ionic surfactants 20 Water 64.96

Example 8.Solid composition Diatomaceous earth Octylbismuth diphenoxide2O Plastics, textiles, paper products and paints are illustrative of thematerials which are rendered resistant to attack when treated byapplying the bismuth compound to the surface and/or by incorporationtherein. The plastics in massive and in fiber form include urethanes,halogenated polymers and copolymers such as polyvinyl chloride andpolyvinyl chloride-acetate copolymers, polyesters, polyamides,polyolefins, and natural and synthetic rubbers. Natural fiber productsthat may be protected include paper products, hemp and felts. Paints maybe rotected in the can and also after application. Typial paints includeinterior and exterior vinyl latex and a kyd paints, the oldernon-synthetic flat natural paints, the acrylics, and the vinyls, andnti-fouligg paints such as the acrylic and the vinyl vali ks thereofi'flie bismuth compounds are also useful in preserving adhesives; insecondary oil recovery processes; in paper mill slime control processes;and in methods of contrplling Staphylococcus aureus in hospitals. Theymay be a useful and active component of detergent sanitizers and may beused for this and other purposes in the form of an aerosol material.They may also be used to protect plants and other growth against attackby microorganisms. Illustrative of resistant paint compositions areExamples 914.

Example 9.-Acrylic anti-fouling paint Parts by weight Titanium dioxide160 Aluminum silicate 48 Talc 12 Methyl methacrylate-butyl methacrylatecopolymer (40% in thinner) 433 Mineral spirits 148 Dibutylbismuthacetate 50 Example 10.Vinyl anti-fouling paint Titanium dioxide 150Bentonite 14 Tricresyl phosphite 1O Vmfidewinyl acetate copolymer resin102 Toluene 223 Methyl isobutyl ketone 295 Triphenylbismuth dichloride35 Phenylbismuth dichloride 35 Example 1 1 .F lat interior paintTitanium-calcium pigment 625 Calcium carbonate 100 Magnesium silicate 25Ester gum solution (60% non-volatile in mineral spirits) 30 Bodiedlinseed oil 200 Mineral spirits 167 Cobalt naphthenate (6% Co) 1 Leadnaphthenate (24% Ph) 2 Phenylbismuth dila-urylmercaptide 6 Example12.Acrylic anti-fouling paint Titanium dioxide 160 Aluminum silicate 48Talc 12 Methyl methacrylate-butyl methacrylate copolymer (40% inthinner) 433 Mineral spirits 148 Butylbismuth dichloride 50 Example13.-Vz'nyl anti-fouling paint Titanium dioxide 150 Bentonite 14Tricresyl phosphite Vinyl chloride vinyl acetate copolymer resin 102Toluene 223 Methyl isobutyl ketone 295 Triphenylbismuth dichloride 35 35Butylbismuth diacet-ate Example 14.-Flat interior paint Titanium-calciumpigment 625 Calcium carbonate Magnesium silicate 25 Ester gum solution(60% non-volatile in mineral spirits) 3 0 Bodied linseed oil 200 Mineralspirits 167 Cobalt naphthenate (6% Co) 1 Lead naphthenate (24% Pb) 2Octylbismuth d-ilaurylmercaptide 6 In each of Examples 15-21, tests arereported showing the activity of the bismuth compounds against notedmicroorganisms, using the potent and toxic phenylmercury acetate as astandard (Example 22). In each example, a series of tests were carriedout when the compound was placed within a nutrient broth in amount of500, 250, 125, 63, 31, 16, 8, 4 and 2 parts per million (p.p.m.). Eachbroth was inoculated with the test organism and the broth incubated at37 C. for two days. The organism growth was visually observed. The brothcontaining the minimum concentration which caused complete inhibition ofthe growth of the organism is tabulated.

Pseudomonas aeruginosa, p.p.m.

Aarobacter aerogenes, p.p.m.

Staph. aareas, ppm.

Example Compound Triphenylbis- 8 31 31 muth dichloride.

Triphenylbis- 16 muth sulfide (crude).

Triphenylbis- 1 8 16 muth diacetate.

Triphenylbis- 1 31 63 muth dimethacrylate.

Diphenylbismuth chloride.

Phenylbismuth dichloride.

Butylbismuth dichloride.

Phenylmercury acetate.

In each of Examples 23-26, tests are reported showing the activity ofthe bismuth compounds against the noted microorganisms. In each examplethe compound was tested using the Agar Diffusion Test, as follows: Thetest compounds were diluted in acetone to obtain the following stocksolutions-5, 2.5, 1.25, 0.63, 0.31%. Filter paper discs, 10 mm. indiameter, were dipped in the test solution and the solvent then allowedto evaporate. AATCC Bacteriostasis agar, held at 45 C., was inoculatedto 1% with an 18-24 hour nutrient broth cultureof Staph. aareus or E.coli. The seeded agar was distributed at the rate of 15 ml./ 10 cm.Petri dish and allowed to solidify. The treated filter paper discs wereplaced on the seeded agar. Then the plates were incubated at 37 C. for48 hours. Inhibition was determined by a zone or halo adjacent to thetreated disc.

EXAMPLE 23 [Zones of inhibition in mm Percent solution S. aureus, mm.

E. coli, mm.

Triphenylbismuth dichloride In each of Examples 27-31, a urethane foamcontaining one of the bismuth compounds was tested against Staph. aureusin the Agar Diffusion Test. The foam composition and results follow:

Parts by Zone of Example weight inhibition,

Polyglycol ether 100 Polysiloxane. 1 Stannous soap 0. 45N-ethyhnorpholine 0. 3 Triethylene diamine 0. 1 Water 2. 9 Tolylenediisoeyanate 38.6 27. Triphenylbismuth dichl de- 0.25 28 Diphenylbismuthchloride 0.1 29 do 0. 30 Phenylbisrnnth dichloride..- 0. 1 31.----- .sd0 0.05

In each of Examples 32-33, a flexible polyvinyl chlo ride plasticcontaining the specified amount of triphenylbismuth dichloride wastested against Staph. aureus in the Agar Diffusion Test.

Parts by Example weight Stearic acid 0 Dioctylphthalate. 0

Polyvinyl chloride resin 0 (Med. molecular weight).

Barium-cadmium salt 2 stabilizer. 32 Triphenylbismuth dichloride- 83 doIn each of Examples 34 and 35, polyvinyl chloride samples with the sameformulation as in Examples 32 and 33, were prepared containing 1 partand 0.5 part of triphenylbismuth dichloride respectively. They weretested for activity against fungi as follows: 1% squares of the plastic,including a plastic control containing none of the bismuth compounds,were placed in Petri dishes containing 30 ml. of a mineral salt Agar.The plastic squares were inoculated with 0.5 ml. of a mixed sporesuspension of Aspergillus niger, Aspergillus flavus, Trichoderma sp.,and Penicillium piscarium. The inoculated samples were incubated at 30C. for 14 days and then visually (and microscopically) examined forfungal growth. There was no growth on the samples prepared with thenoted amounts of the bismuth compound. The plastic control exhibitedmoderate growth.

The following compounds are given as further examples of bismuthcompounds employed in the compositions and methods of the invention andit will be understood that such compounds (as well as the othercompounds herein set forthlmay be used in place of the various compoundsspecifically shown in the foregoing examples.

Triphenylbismuth sulfide Triphenylbismuth diacetate Triphenylbismuthdimethacrylate Triphenylbismuth oxide Triphenylbismuth difluorideTriphenylbismuth dibromide Triphenylbismu-th dihydroxideTriphenylbismuth (hydroxy) chloride Triphen'ylbismuth (chloro acetateTriphenylbismuth dicyanide Trianisylbisrnuth dichlorideTribromophenylbismuth dichloride Ti chlorophenylbismuth dichlorideTri-a-naphthylbismuth dichloride Trinitrophenylbismuth dichlorideTritolylbismuth dichloride Trixylylbismuth dibromide T ribiphenylbismuthdichloride Diphenyl-p-tolylbismuth dichloride Tri-p-tolylbismuthdiacetate Triphenylbismuth dibenzoate Triphenylbismuthmercaptopropionate Tri-p-tolylbismuth dibenzoate Tri-o-tolylbismuthdisalicylate C H Triphenylbismuth disaiicyla-te Triphenylbismuthdi-p-hydroxybenzoate Triphenylbismuth di-p-aminobenzoateTriphenylbismuth di-p-aminobenzoate -2CH COCH Triphenylbismuthdichloroacetate Trip'henylbismuth ditartrate Triphcnylbismuthdiphenoxide Triphenylbismuth dilaurylmercaptide Triphenylbismuthdibutoxide Tritolylbismuth di-o-phenylphenate Tritolylbismuth S,S-bisisooctylmercaptoacetate Tritolylbismuth diethoxide Octylbismuth sulfideButylbismuth sulfide Dibutylbismuth acetate Butylbismuth dibenzoateDibutylbismuth methacrylate Butyl-bismuth diacrylate Dibutylbismuthphenate Butylbismuth mercaptopropionate Dibutylbismuth laurylmercaptideDibutylbismuth isooctylmercaptoacetate Butylbismuth bis-o-phenylphenateDiphenylbismuth chloride Di-p-chlorophenylbismuth chlorideDi-p-chlorophenylbismuth bromide Di-p-chlorophenylbismuth iodideDiphenylbismuth chloride Diphenylbismuth iodide Diphenylbismuth cyanideDiphenylbismuth hydroxide Diphenylbismuth thiocyanate Di-p-tolylbismuthchloride Dicyclohexylbismuth chloride Cyclopentylbismuth diacetateVinylphenylbismuth dichloride Phenylbismuth dibromidep-Chlorophenylbismuth dibromide p-Tolylbismuth dichloride Diethylbismuthbromide Dibutenylbismuth chloride Diallylbismuth acetate Dimethylbismuthchloride Vinylbismuth dichloride Dimethylbismuth hydroxide Methylbismuthdichloride Methylbismuth oxide Butylbismuth sulfide Butyl-bismuth oxideButylbismuth dichloride Ethylbismuth dichloride Butylbismuth dibromideDibutylbismuth cyanide Those skilled in the art will appreciate thatother organobismuth compounds as defined herein can be employed in thecompositions and methods of the invention to protect a wide variety ofmaterials and living organisms that are susceptible to attack bymicroorganisms.

As is well known to those skilled in the art, the compounds which may beused in practice of this invention may be synthesized by well knowntechniques and are readily obtainable. As many embodiments of thisinvention may be made without departing from the spirit and scopethereof, it is to be understood that the invention includes all suchmodifications as come within the scope of the appended claims.

I claim:

1. A method for protecting a medium susceptible to attack bymicroorganisms which comprises applying to the locus to be protected aneffective amount of a hismuth compound RBiX wherein X is selected fromthe group consisting of halogen, oxygen, sulfur, carboxylate, phenoxide,alkoxide, mercaptide, and cyanide, and R is lower alkyl.

2. A method for protecting a medium susceptible to attack bymicroorganisms as claimed in claim 1 wherein R is butyl.

3. A method for protecting a medium susceptible to attack bymicroorganisms as claimed in claim 1 wherein X is chloride.

4. A method for protecting a medium susceptible to attack bymicroorganisms as claimed in claim 1 wherein the bismuth compound RBiXis butylbismuth dichloride.

5. A method for protecting a medium susceptible to attack bymicroorganisms which comprises applying to the locus to be protected aneffective amount of (a) a bismuth compound RBiX wherein X is selectedfrom the group consisting of halogen, oxygen, sulfur, carboxylate,phenoxide, alkoxide, mercaptide, and cyanide, and R is lower alkyl; and(b) a compound R" NH 'A wherein R" is a hydrocarbon radical, A is ananion of a complexforming acid, c is an integer 1-4, d is an integer -3,and the sum of c and d is 4.

6. A composition comprising an inert carrier, as the active component abactericidal amount of 0.02%% by weight of a bismuth compound RBiXwherein X is selected from the group consisting of halogen, oxygen,sulfur, carboxylate, phenoxide, alkoXide, mercaptide, and cyanide, and Ris lower alkyl, and a dispersing agent.

7. A composition as claimed in claim 6 wherein R is butyl.

8. A composition as claimed in claim 6 wherein X is chloride.

9. A composition as claimed in claim 6 wherein the bismuth compound RBiXis butylbismuth dichloride.

10. A composition comprising a carrier and, as the active component abactericidal amount of (a) 0.1%- 10% by weight of a bismuth compoundRBiX wherein X is selected from the group consisting of halogen, oxygen,sulfur, car-boxylate, phenoxide, alkoxide, mercaptide, and cyanide, andR is lower alkyl; and (b) a compound R" ,NH -A wherein R" is ahydrocarbon radical, A is an anion of a complex-forming acid, 0 is aninteger 1-4, d is an integer 0-3, and the sum of c and d is 4.

11. A composition comprising an inert carrier, as the active component0.1%10% by weight of a bismuth compound RBiX wherein X is selected fromthe group consisting of halogen, oxygen, sulfur, carboxylate, phen- 10oxide, alkoxide, mercaptide, and cyanide, and R is lower alkyl, and adispersing agent.

12. A microorganism resistant paint comprising a paint composition andan effective amount or" a bismuth compound RBiX wherein X is selectedfrom the group consisting of halogen, oxygen, sulfur, carboxylate,phenoxide, alkoxide, mercaptide, and cyanide, and R is lower alkyl.

13. A microorganism resistant paint as claimed in claim 12 comprising apaint composition and an effective amount of butylbismuth dichloride. (1

14. A microorganism resistant plastic material comprising a plasticcomposition and an effective amount of a bismuth compound RBiX wherein Xis selected from the group consisting of halogen, oxygen, sulfur,carboxylate, phenoxide, alkoxide, 'mercaptide, and cyanide, and R islower alkyl.

15. A microorganism resistant urethane comprising a urethane and aneffective amount of a bismuth compound RBiX wherein X is selected fromthe group consisting of halogen, oxygen, sulfur, carboxylate, phenoxide,alkoxide, mercaptide, and cyanide, and R is lower alkyl.

16. A microorganism resistant paper comprising paper and an effectiveamount of a bismuth compound RBiX wherein X is selected from the groupconsisting of halogen, oxygen, sulfur, carboxylate, phenoxide, alkoxide,mercaptide, and cyanide, and R is lower alkyl.

17. A microorganism resistant cloth comprising cloth and an effectiveamount of a bismuth compound RBiX wherein X is selected from the groupconsisting of halogen, oxygen, sulfur, carboxylate, phenoxide, alkoxide,mercaptide, and cyanide, and R is lower alkyl.

18. A bacteriostatic aerosol composition comprising a carrier, apropellant, and as the active component a bismuth compound RBiX whereinX is selected from the group consisting of halogen, oxygen, sulfur,carboxylate, phenoxide, alkoxide, mercaptide, and cyanide, and R islower alkyl.

19. A method of treating a hospital to minimize the incidence of Staph.aureus which comprises applying to filters, room surfaces, and cloth aneffective amount of a bismuth compound RBiX wherein X is selected fromthe group consisting of halogen, oxygen, sulfur, carboxylate, phenoxide,alkoxide, mercaptide, and cyanide, and R is lower alkyl.

20. A composition comprising a solid inert carrier and, as the activecomponent a germicidal amount of a hismuth compound RBiX wherein X isselected from the group consisting of halogen, oxygen, sulfur,carboxylate, phenoxide, alkoxide, mercaptide, and cyanide and R is loweralkyl.

References Cited by the Examiner UNITED STATES PATENTS 2,113,567 4/1938Andersen 167-30 2,114,012 4/1938 Andersen 167-30 2,191,922 2/1940 Bruson16730 2,284,126 5/1942 Bruson 16768 2,423,262 7/1947 Sowa 167302,555,114 5/1951 Bywater et al 260-433 3,058,877 10/1962 Musser 16738.5X

OTHER REFERENCES Coates, Organo-Metallic Compounds, John Wiley & Sons,Inc., New York, 1956, pages 227-232.

Gilman et al., Chem. Rev., vol. 30, 1942, pages 301- 303.

JULIAN S. LEVITT, Primary Examiner.

GEORGE A. MENTIS, Assistant Examiner.

1. A METHOD FOR PROTECTING A MEDIUM SUSCEPTIBLE TO ATTACK BYMICROORGANISMS WHICH COMPRISES APPLYING TO THE LOCUS TO BE PROTECTED ANEFFECTIVE AMOUNT OF A BISMUTH COMPOUND RBIX2 WHEREIN X IS SELECTED FROMTHE GROUP CONSISTING OF HALOGEN, OXYGEN, SULFUR, CARBOXYLATE, PHENOXIDE,ALKOXIDE, MERCAPTIDE, AND CYANIDE, AND R IS LOWER ALKYL.